RESOURCE GEOLOGY, vol. 55, no.

2, 73–90, 2005

Evolution of Hydrothermal System at the Dizon Porphyry

Cu-Au Deposit, Zambales, Philippines

Akira IMAI*

Department of Earth and Planetary Science, University of Tokyo

* Present address: Department of Earth Resources Engineering, Graduate School of Engineering, Kyushu
University, 6-10-1 Hakozaki, Fukuoka 812-8581, Japan [E-mail: imai@mine.kyushu-u.ac.jp]
Received on June 4, 2004; accepted June 14, 2005

Abstract: Evolution of hydrothermal system from initial porphyry Cu mineralization to overlapping epithermal system at the
Dizon porphyry Cu-Au deposit in western central Luzon, Zambales, Philippines, is documented in terms of mineral paragen-
esis, fluid inclusion petrography and microthermometry, and sulfur isotope systematics.
The paragenetic stages throughout the deposit are summarized as follows; 1) stockwork amethystic quartz veinlets associ-
ated with chalcopyrite, bornite, magnetite and Au enveloped by chlorite alteration overprinting biotite alteration, 2) stockwork
quartz veinlets with chalcopyrite and pyrite associated with Au and chalcopyrite and pyrite stringers in sericite alteration, 3)
stringer quartz veinlets associated with molybdenite in sericite alteration, and 4) WNW-trending quartz veins associated with
sphalerite and galena at deeper part, while enargite and stibnite at shallower levels associated with advanced argillic alteration.
Chalcopyrite and bornite associated with magnetite in quartz veinlet stockwork (stage 1) have precipitated initially as
intermediate solid solution (iss) and bornite solid solution (bnss), respectively. Fluid inclusions in the stockwork veinlet quartz
consist of gas-rich inclusions and polyphase inclusions. Halite in polyphase inclusions dissolves at temperatures ranging from
360°C to >500°C but liquid (brine) and gas (vapor) do not homogenize at <500°C. The maximum pressure and minimum temper-
ature during the deposition of iss and bnss with stockwork quartz veinlets are estimated to be 460 bars and 500°C.
Fluid inclusions in veinlet stockwork quartz enveloped in sericite alteration (stage 2) consist mainly of gas-rich inclu-
sions and polyphase inclusions. In addition to the possible presence of saturated NaCl crystals at the time of entrapment of
fluid inclusions that exhibit the liquid-vapor homogenization temperatures lower than the halite dissolution temperatures in
some samples, wide range of temperatures of halite dissolution and liquid-vapor homogenization of polyphase inclusions
from 230°C to >500°C and from 270°C to >500°C, respectively, suggests heterogeneous entrapment of gaseous vapor and
hypersaline brine. The minimum pressure and temperature are estimated to be about 25 bars and 245°C.
Fluid inclusions in veinlet quartz associated with molybdenite (stage 3) are dominated by gas-rich inclusions accom-
panied with minor liquid-rich inclusions that homogenize at temperatures between 350°C and 490°C.
Fluid inclusions in vuggy veinlet quartz associated with stibnite (stage 4) consist mainly of gas-rich inclusions with
subordinate polyphase inclusions that do not homogenize below 500°C. Fluid inclusions in veinlet quartz associated with
galena and sphalerite (stage 4) are composed of liquid-rich two-phase inclusions, and they homogenize into liquid phase at
temperatures ranging widely from 190°C to 300°C (suggesting boiling) and the salinity ranges from 1.0 wt% to 3.4 wt%
NaCl equivalent. A pressure of about 15 bars is estimated for the dilute aqueous solution of 190°C from which veinlet quartz
associated with galena and sphalerite precipitated.
In addition to a change in temperature-pressure regime from lithostatic pressure during the deposition of iss and bnss
with stockwork quartz veinlets to hydrostatic pressure during fracture-controlled quartz veinlet associated with galena and
sphalerite, a decrease in pressure is supposed to have occurred due to unroofing or removal of the overlying piles during the
temperature decrease in the evolution of hydrothermal system.
The majority of the sulfur isotopic composition of sulfides ranges from ±0 ‰ to +5 ‰. Sulfur originated from an iso-
topically uniform and homogeneous source, and the mineralization occurred in a single hydrothermal system.
Keywords: Dizon, porphyry Cu deposit, Philippines, Luzon, fluid inclusion, hydrothermal system, sulfur isotope

1982, 1986; Sillitoe and Gappe, 1984; Imai, 2002). The

1. Introduction
The Dizon deposit has been known as one of repre-
sentative Au-rich porphyry Cu deposits in the western
Luzon arc, Philippines (Bureau of Mines and Geo-
sciences (BMG), 1982, 1986; Sillitoe and Gappe,
1984). Geologic documentations were made by Malihan
(1982, 1987) and Aquino (1993), and the outline of the
deposit has been described in some articles (BMG,
Dizon porphyry Cu-Au deposit has been considered as a
representative area to show a linkage between porphyry
and epithermal mineralizations, for an advanced argillic
alteration blanket associated with high sulfidation
assemblage and for post-ore pebble dikes and dia-
tremes. In this paper, the evolution of hydrothermal sys-
tem is documented in terms of mineral paragenesis,
fluid inclusion petrography and microthermometry, and
sulfur isotope systematics.

73
74
Porphyry Cu deposit Trench
Quaternary volcano Fault (dashed where inferred)
Intermediate - silicic intrusive rocks
Ophiolitic rocks
Fig. 1 Map showing locality of the Dizon porphyry Cu-Au deposit and other
major porphyry Cu deposits in the Luzon, Philippines, with distribution of
Quaternary volcanoes, Neogene silicic-intermediate intrusive rocks and
ophiolitic complexes (modified after Bureau of Mines and Geosciences,
1982, 1986; Imai, 2001).
2. Geologic Background
The Philippine archipelago is situated in the western
Pacific rim along the plate converging margin, being sub-
ducted both at the Manila trench in the west and at the
Philippine trench in the east (Fig. 1) (e.g., Yang et al.,
1996). A number of porphyry Cu deposits have been
formed through the Cenozoic in the island arc setting in
the Philippines (Sillitoe and Gappe, 1984; Zanoria et al.,
1984; BMG, 1986; Imai, 2002). A chain of porphyry Cu
deposits of the western Luzon arc (Fig. 1) includes the
Lepanto-Far Southeast (FSE) (Concepcíon and Cinco,
1989; Hedenquist et al., 1998; Imai, 2000b), the Guina-
oang (Tirad) (Sillitoe and Angeles, 1985), the Lobo and
Boneng (Jacinto, 1977), the Santo Niño (Bryner, 1970),
Akira IMAI RESOURCE GEOLOGY :
the Black Mountain (Kennon) (Toñgonan,
1977), and the Santo Tomas II deposit
(Serafica and Baluda, 1977; Togashi et
al., 1990; Piestrzynski et al., 1994;
Tarkian and Koopmann, 1995; Imai,
2001) deposits of the western flank of the
Philippine Central Cordillera in northern
Luzon, the Dizon deposit (Malihan, 1982,
1987; Aquino, 1993) in the central west-
ern Luzon, and the Taysan deposit (Wolfe
et al., 1978) in the southern western
Luzon (Fig. 1). These porphyry-type
deposits are genetically associated with
intermediate to silicic intrusions, that
comprise the ancient western Luzon mag-
matic arc initiated by eastward subduction
of South China Sea (e.g., Mitchell and
Leach, 1991). The intermediate to silicic
igneous rocks associated with porphyry-
type Cu deposits in the western Luzon arc
are characterized by high SO3 contents
(>0.1 wt % as SO3) of their microphe-
nocrystic igneous accessory apatite, sug-
gesting that sulfur has been accommodat-
ed dominantly as oxidized species under
oxidizing condition in the intermediate to
silicic hydrous magmas (Imai, 2002,
2004).
The Dizon deposit is located on the
western flank of southwestern Zambales-
Bataan volcanic range hugging the south-
eastern edge of the Zambales. The host
rocks to the intrusions at the Dizon
deposit are Neogene subaerial volcani-
clastics overlying the Zambales ophiolite
complex (Fig. 1) (Malihan, 1982, 1987).
A K-Ar age determined on the potassi-
cally altered fine-grained diorite porphyry
from the orebody center, which is
exposed at the bottom of the open pit yielded 2.5±0.2 Ma
(Imai, 2002). This is consistent with the age of 2.7 Ma
determined on hydrothermal sericite (Malihan, 1987).
3. Outline of the Dizon Deposit
The following description of the outline of the Dizon
deposit is summarized from Malihan (1987). The Dizon
mine was operated by Benguet Corporation by an open pit
for Cu and substantial quantities of Au and Ag as by prod-
ucts. The deposit has been estimated to contain at 0.20 %
Cu cut off some 187 million tons of reserves with metal
contents averaging 0.355 % Cu, 0.746 g/t Au and about
2.0 g/t Ag. The Dizon deposit is located within the munic-
ipality of San Marcelino, Zambales, about 80 km north-
vol. 55, no. 2, 2005 Dizon Porphyry Cu-Au Deposit, Philippines 75

veinlets, fracture filling

stringers and dissemina-
tions. Ore grade mineral-
ization is hosted mainly in
the potassic (biotite) and
phyllic (sericite) zones of
hydrothermal alteration
(Fig. 2). The most abun-
dant Cu mineral is chal-
copyrite followed by bor-
nite. Gold and silver also
appear to be intimately
associated with Cu sul-
fides. Late stage WNW-
trending fault veins which
carry variable amount of
sphalerite, galena, tetra-
hedrite and stibnite cut
across the porphyry sys-
tem (Figs. 2, 3). Enargite
is found at a shallower
portion of these veins
accompanying advanced
argillic alteration marked
by alunite and kaolinite.
These structures also carry
appreciable Ag values but
its Au contents are consid-
ered insignificant. The
advanced argillic alter-
ation blanket spread wide-
ly surrounds the deposit
(Fig. 2). The southern part
of the deposit was largely
destroyed by the post ore
Propylitic (chlorite/epidote) Agglomerate (Pleistocene) “Pua Diatreme”, in addi-
Propylitic (chlorite/epidote) Fault
Advanced argillic (quartz/kaolinite/alunite) Hydrothermal breccia/pebble dike tion to the irregular bodies
Advanced argillic (quartz/kaolinite/alunite)
Advanced argillic (quartz/pyrophyllite/diaspore)
Advanced argillic (quartz/pyrophyllite/diaspore)
Silicified zone Dacite porphyry of pebble dikes (Figs. 2,
Phyllic-argillic (quartz/sericite/sericite-smectite)
Phyllic-argillic (quartz/sericite/sericite-smectite) Outline of orebody Pua diatreme 3). In addition to the
Potassic (quartz/biotite/chlorite)
Potassic (quartz/biotite/chlorite) Welded breccia quartz diorite porphyry,
Pit limit (0.2%Cu cut off)
Boundary of alteration zonezone Quartz diorite Malihan (1987) described
Boundary of alteration
Road Quartz diorite porphyry
Fig. 2 Geology and alteration map “microdiorite” distributed
Creek, drainage Diorite
of the Dizon mine and the vicin- Basal volcanics (Late Miocene)
in the north outside the
ity (modified after Malihan, Building orebody, “intra-mineral
Geologic boundary
1987). quartz diorite” in the
southern part of the ore-
west of Manila. It lies about 19 km from the central cone body (Figs. 2, 3), and “post-mineral dacite” dikes in the
of Mount Pinatubo erupted in 1991. surrounding area (Fig. 2).
Mineralization at the Dizon deposit is genetically
related to a small, steeply dipping quartz diorite porphyry 4. Analytical Procedures
stock that intruded volcanic rocks presumably of Late
Miocene age (Fig. 2). The mineralization is hosted mainly Chemical composition of minerals has been determined
by the quartz diorite porphyry and to a lesser degree by by wave-length dispersive electron probe microanalyzer,
the volcanic wall rocks and consists of stockwork quartz JEOL JCMA 733mkII. Chemical composition of metallic
76 Akira IMAI RESOURCE GEOLOGY :

(1997).
Fluid inclusion microthermome-
try has been done in terms of heat-
ing-freezing experiments using an
USGS adopted Fluid Inc. heating/
freezing stage. The highest tempera-
ture of current working condition
was placed at 500°C.
Sulfur isotopic ratios were deter-
mined for sulfides and sulfates.
Preparation was done according to
procedure described by Yanagisawa
and Sakai (1983): sulfur of sulfides
were converted to sulfate by HNO3
+Br2, then fixed as BaSO4 (barite)
and the SO 2 (gas) was liberated
from barite converted from sulfides
as well as barite converted from
gypsum by heating with V2O5 and
SiO2 in a vacuumed glass line. The
sulfur isotopic ratio was determined
for the SO2 on FinniganMAT delta
E mass spectrometer. The isotopic
compositions are presented in con-
ventional δ34S per mil (‰) expres-
sion. The overall accuracy is esti-
mated within ±0.2 ‰ based on sta-
tistical data of the laboratory.

5. Intrusive Rocks at the Dizon

Deposit
Hydrothermal breccia/pebble dike
As mentioned in the previous
Dacite porphry chapter, four types of intrusive
Sample locality
Pua diatreme rocks have been described at the
Welded breccia Dizon deposit (Malihan, 1982,
Bench
Quartz diorite 1987), namely “pre-mineralization
Mine level
Quartz diorite porphyry
microdiorite (referred to as diorite
hereafter)” distributed in the north
Vein Diorite
outside the orebody, “quartz diorite
Geologic boundary Basal volcanic rocks
porphyry”, “intra-mineral quartz
Fig. 3 Geologic plan map of the Dizon deposit, showing the locality of samples diorite (referred to as quartz diorite
mentioned in this paper (modified after Benguet Corporation unpublished data). hereafter)” in the southern part of
the orebody, and “post-mineral
minerals such as native gold/electrum and tetrahedrite dacite porphyry (referred to as dacite porphyry hereafter)”
group minerals was analyzed with acquisition time of 30 dikes in the surrounding area (Figs. 2, 3). Summary of pet-
seconds for each element, with background counted for 15 rography on major rock-forming minerals of intrusive
seconds at both sides at 25 kV and 2.0 × 10-8A specimen rocks is presented in Table 1. Whole-rock compositions of
current. The results were computed by conventional ZAF least altered diorite, quartz diorite porphyry and dacite
calculation using factors and program supplied by JEOL. porphyry are presented in Table 2, whereas that of quartz
Whole-rock compositions were determined by means diorite is not determined because the least altered one was
of X-ray fluorescence spectrometer using a Philips not obtained in this work.
PW1480. Major element oxides and trace element concen-
5.1. Diorite
trations were determined on a fused glass bead, according
to the procedure described by Tanaka and Orihashi Diorite is a medium-grained holocrystalline granular
vol. 55, no. 2, 2005 Dizon Porphyry Cu-Au Deposit, Philippines 77

Table 1 Intrusive rocks at the Dizon porphyry Cu-Au deposit.

phenocryst (abundance and size, mm) groundmass
Rock type remarks
plagioclase hornblende biotite quartz (size, mm)
(pre-mineralization)
diorite +++ ++ ± +/± equigranular
<2.5 <2.5 <0.3 <0.3
quartz diorite porphyry ++ ++/+ - ± medium-grained intergtranular goundmass
<3.5 <2.5 <1.0 <0.2
(intra-mineralization)
quartz diorite +++ ++ + ++/+ equigranular
<2.5 <2.0 <0.6 <0.3
(post mineralization)
dacite porphyry +++/++ ++/+ - ± fine-grained rare quartz phenocrysts
<6.0 <4.0 <3.0 <0.1
Abundance of phenocrystic mineral is presented semi-quantitatively.
+++: abundant (>30 % volume), ++: major (30> >10 %), +: minor (10> >1 %), ±: rare/trace (<1 %), -: not present.

Table 2 Whole-rock composition of least-altered intru- mineralization. Hornblende is often altered hydrothermal-
sive rocks at the Dizon porphyry Cu-Au deposit. ly and replaced by chlorite and tremolite-actinolite.
Sample ID 011220 031103 011107 Occasionally tourmaline is observed as a radial aggregate
quartz diorite dacite in diorite, which is considered as an alteration product.
Rock type porphyry diorite porphyry
SiO2(wt%) 61.9 53.6 63.9 5.2. Quartz diorite porphyry
TiO2 0.5 0.8 0.5
Al2O3 15.9 18.2 16.8 Quartz diorite porphyry intrusion hosts bulk of the
Fe2O3 6.5 9.7 4.4 orebody at the Dizon deposit, and is exposed in the cen-
MnO 0.1 0.4 0.1 tral part of the open pit (Fig. 3). It consists mainly of
MgO 2.0 4.6 1.4 phenocrysts of sub- to euhedral plagioclase (up to 3.5
CaO 5.4 8.1 6.4 mm across) and hornblende (up to 2.5 mm long) with
Na2O 5.0 3.7 3.8
K2O 0.6 0.2 1.4 trace of phenocrystic high-temperature granular quartz
P2O5 0.2 0.2 0.2 (less than 1.0 mm across) in intergranular groundmass
total 98.1 99.5 98.9 mainly consisting of granular quartz and plagioclase.
Ba(ppm) 168.4 111.2 302.9 Within the orebody, hornblende is commonly replaced
Co 12.7 9.7 8.3 by polycrystalline aggregate of shredded biotite, where-
Cr 20.3 31.3 15.8 as chlorite and sericite alterations are also widespread.
Ga 17.1 19.9 17.7
Nb 2.8 2.3 4.3 5.3. Quartz diorite
Ni 10.8 17.5 10.1
Rb 12.3 4.6 31.6 Malihan (1982, 1987) described the quartz diorite
Sr 474.6 712.2 607.2 body as an intra-mineralization intrusive rock. It is a
V 92.1 255.8 95.1 medium-grained holocrystalline granular rock under the
Y 15.1 19.0 13.5
Zr 84.4 63.9 93.8
microscope. It consists mainly of an- to subhedral pla-
Ce 10.0 15.4 22.1 gioclase (up to 2.5 mm across) and sub- to euhedral
La 7.0 7.8 13.1 hornblende (up to 2.0 mm long) with subordinate
Pb 8.8 5.8 6.8 amount of quartz (less than 0.3 mm across) that fill
Sc 14.1 28.4 14.1 interstices between hornblende and plagioclase, and
Zn 94.6 95.7 52.4
Th 3.9 2.7 4.7
small amount of flakes of biotite (less than 0.6 mm
Sr/Y 31.3 37.6 44.9 across). The diorite body is exposed in the southern part
taken from Imai (2002). of the open pit (Fig. 3). Within the orebody, hornblende
is often replaced by polycrystalline aggregate of shred-
rock under the microscope. It consists mainly of an- to ded biotite due to hydrothermal alteration, whereas
subhedral plagioclase (up to 2.5 mm across) and sub- to chlorite and sericite alterations are also widespread.
euhedral hornblende (up to 2.5 mm long) with small
5.4. Dacite porphyry
amount of quartz (less than 0.3 mm across) that fill inter-
stices between hornblende and plagioclase. In addition, A columnar-jointed large body (up to 200 m across)
trace of biotite (less than 0.3 mm across) is also found. of dacite porphyry appears as a large block in the Pua
The diorite body is exposed to north outside of the open Diatreme (Fig. 3). It consists mainly of phenocrysts of
pit (Fig. 3), and it is regarded to have intruded prior to euhedral plagioclase (up to 6.0 mm across) and horn-
78 Akira IMAI RESOURCE GEOLOGY :

blende (up to 4.0 mm long) with trace of phenocrystic

granular quartz (less than 3.0 mm across) in very fine-
grained cryptocrystalline groundmass. Alteration of the
dacite pophyry is not significant, whereas calcite occurs
as partial replacement of hornblende and plagioclase
phenocrysts and in groundmass.

6. Ore Petrography and Paragenesis

Whereas phyllic (sericite) alteration and sericite-chlo-

rite-clay (SCC) alteration (Sillitoe and Gappe, 1984) are
widespread in the deposit, potassic alteration character-
ized by the polycrystalline aggregate of shredded sec-
ondary biotite that replaced phenocrystic hornblende in
the intrusive rocks is present in the deeper and central
part of the deposit (Fig. 2). The overprinting of chlorite
alteration on the potassic alteration was recognized by
the envelope of chlorite alteration along veins and
stringer veinlets (Fig. 4A) as described at Mamut (Imai,
2000a) and Lapanto-FSE (Imai, 2000b).
The paragenetic stages throughout the deposit are
summarized as follows; 1) stockwork amethystic quartz
veinlets associated with chalcopyrite-bornite-magnetite Fig. 4 Photographs of representative samples, (A): Enve-
and Au in chlorite alteration envelope, 2) stockwork lope of chlorite alteration (chl) along stringer quartz
quartz veinlets with chalcopyrite and pyrite “center- veinlets (str) overprinting the potassic alteration in
line” associated with Au and chalcopyrite and pyrite diorite (#13324, 225 level, north-center); (B): stock-
work amethystic quartz veinlets (vn) associated with
stringers in sericite alteration, 3) stringer quartz veinlet
magnetite, chalcopyrite and bornite in quartz diorite
associated with molybdenite in sericite alteration and 4) porphyry. Quartz veinlets do not show “center-line”
WNW-trending quartz veins associated with sphalerite, structure (#041104, 237.5 level, southwest).
galena, enargite and stibnite.
6.1. Stockwork amethystic quartz veinlets associated with nite (Fig. 5B). Magnetite grains are often partly replaced
chalcopyrite-bornite-magnetite and Au in chlorite by hematite along their boundaries (Fig. 5C), whereas
alteration envelope (stage 1) occasionally bornite is also replaced by aggregate of
minute flakes of covellite (Fig. 5C) of supergene origin.
At the central part of the open pit, irregular stockwork
amethystic quartz veinlets <1 cm wide (Fig. 4B) is devel- 6.2. Stockwork quartz veinlet with chalcopyrite and pyrite
oped and hosts the principal Cu-Au mineralization. “center-line” and chalcopyrite and pyrite stringers
Quartz veinlets occur as almost vertical, parallel, sheeted in sericite alteration (stage 2)
veinlets in the southwestern part of the bottom of the open
Along the southeastern and southwestern walls in the
pit. These stockwork and sheeted quartz veinlets are usu-
open pit (Fig. 3), stockwork of quartz veinlets <2 cm wide
ally enveloped by chlorite alteration presently. Quartz in
(Fig. 6A) having “center-line” of chalcopyrite, pyrite and
the veinlet are granular usually <0.1 mm in diameter. The
marcasite (Fig. 6B) associated with sericite alteration halo
veinlets do not show “center-line” structure (Fig. 4B),
are widely developed. The “center-line” has been com-
while granular magnetite associated with lesser amount of
monly used for the mode of occurrence of sulfides that fill
chalcopyrite and bornite are locally concentrated along
a planar vug at the center of quartz veinlets from porphyry
the margin of some parts of these veinlets. Opaque miner-
Cu deposit (e.g., Batu Hijau deposit: Arif and Baker,
al assemblage in the quartz veinlets and in the host rocks
2004).
adjacent to the quartz veinlets consists of chalcopyrite,
Such stockwork quartz veinlets enveloped in sericite
bornite and magnetite. Chalcopyrite and bornite often
alteration comprise high-grade Cu-Au ore in the north-
exhibit micrographic intergrowth texture, and chalcopy-
western part (Fig. 3) at the relatively deep portion
rite hosts lamellae of bornite (Fig. 5A), whereas coarse-
(between 225.5 m and 275 m level). Quartz sometimes
grained chalcopyrite and bornite without lamellae inter-
appears chalcedonic-porcellaneous, and marcasite occurs
growth are also common. Minute blebs of native gold/Au-
locally along with pyrite and chalcopyrite in quartz vein-
rich electrum occur as inclusions in chalcopyrite and bor-
vol. 55, no. 2, 2005 Dizon Porphyry Cu-Au Deposit, Philippines
Fig. 5 Photomicrographs showing representative ore tex-
tures from the principal Cu-Fe sulfide ores of the
Dizon porphyry Cu-Au deposit. (A): Bornite (bn) and
chalcopyrite (cp) exhibiting micrographic intergrowth
in magnetite (mt)-bearing amethystic quartz (qz) vein-
let. Bornite is partly replaced by lath-shaped covellite
(cv) (#041104, 237.5 level southwest); (B): A minute
bleb of native gold/Au-rich electrum (Au) associated
with bornite (bn) and chalcopyrite (cp) exhibiting
micrographic intergrowth texture in magnetite-bearing
amethystic quartz (qz) veinlet. (#041104, 237.5 level
southwest); (C): Bornite (bn), chalcopyrite (cp) and
magnetite (mt) in amethystic quartz (qz) veinlet.
(#041104, 237.5 level southwest). Bornite is extensive-
ly replaced by aggregate of lath-shaped covellite (cv),
whereas magnetite is partially replaced by minute
blebs of hematite and maghemite (hm).
79
Fig. 6 Photographs of representative samples of ores asso-
ciated with sericite alteration envelope in the Dizon
deposit. (A): Marcasite, pyrite and chalcopyrite-bearing
stockwork quartz veinlet (vn) associated with sericite
alteration envelope. Some quartz veinlet is associated
with “center-line” (cl) of marcasite, pyrite and chalcopy-
rite (#021220, 275 level, west), (B): Stockwork quartz
veinlet (vn) with “center-line” (cl) of marcasite, pyrite
and chalcopyrite associated with sericite alteration enve-
lope. Stockwork quartz veinlet is cut by stringer quartz
veinlet (str) with “center-line” (cl) of marcasite, pyrite
and chalcopyrite (#021220, 275 level, west).
let stockwork in the sericite alteration envelope.
Veinlets of quartz are locally drusy or vuggy. The “cen-
ter-line” in the stockwork quartz veinlets and stringers
are often dominated by pyrite with scarce chalcopyrite,
whereas they are dominated by chalcopyrite in some
cases. The grain size of chalcopyrite and pyrite is usual-
ly <1 mm, whereas occasionally >5 mm. In addition,
stringer veinlets of chalcopyrite and/or pyrite that post-
dated the stockwork quartz veinlets along fracture
planes are also extensively developed.
In the northern part of the open pit, an irregular
cupriferous sulfide veinlet up to 2 cm wide was recog-
nized (#10324, Fig. 3). The veinlet seemed to be a vari-
80 Akira IMAI RESOURCE GEOLOGY :

Table 3 Chemical composition of native gold, Dizon porphyry Cu-Au deposit. 6.3. Stringer quartz veinlet asso-
wt% atom% ciated with molybdenite in
Sample ID
Au Ag Cu Fe total Au Ag Cu Fe total sericite alteration (stage 3)
10324 91.96 7.58 0.13 0.23 99.90 85.94 12.93 0.37 0.76 100.00
In the present study, only one
Determined by electron probe microanalyzer, JEOL JCMA 733 markII, using accelerating
occurrence of molybdenite has
voltage of 25 kV and probe current of 2.0×10-8 A. The results were calibrated by conventional
ZAF correction. been observed. Hexagonal
Sample Description: flakes of molybdenite <2 mm
10324: Native gold associated with pyrite in marcasite, pyrite and chalcopyrite-bearing across are associated with a nar-
stockwork quartz veinlet in sericite alteration envelope (222.5 level, north). row quartz veinlet, enveloped
by sericite alteration at the west-
ern wall of the open pit (#071106; Fig. 3). Temporal rela-
tionships between molybdenite and other alteration and
mineralization are uncertain, while Malihan (1987)
included the molybdenite mineralization into the same
period of the stibnite and enargite mineralization.
6.4. WNW-trending quartz veins associated with spha-
lerite, galena, enargite and stibnite (stage 4)
Swarm of WNW-trending fractures cut across the cen-
tral part of the ore deposit in the open pit. Some of these
fractures grade into the lens shaped pebble dikes in the
eastern part in the pit. Coarse-grained (>5 cm locally)
gypsum associated with pyrite occurs as irregular veinlets
in the matrix of pebble dikes.
In the northern part of the pit, these fractures are
filled with drusy quartz veins < 10cm wide associated
with Pb-Zn mineralizations (Fig. 3). In these veins,
galena, sphalerite and tetrahedrite group mineral (ten-
nantite; Table 4) are dominant ore constituents. Under
the microscope, minute micrographic-myrmekitic inclu-
sions of tennantite within the galena grains are often
observed. Vein quartz is often fine-grained, grayish in
color megascopically, appearing chalcedonic, and crus-
tiform/banded, and botryoidal habit on the vugs of crus-
Fig. 7 Photomicrographs showing representative ores asso-
ciated with sericite alteration envelope in the Dizon tiform banded veins.
deposit. (A): A minute bleb of native gold (Au) is During the early stage of mine development, the con-
attached to coarse-grained idiomorphic pyrite (py) in tinuation of these fractures at the shallow part of the
chalcopyrite (cp) in stockwork quartz veinlet associated deposit were recognized to be related to advanced argillic
with sericite alteration envelope (#10324, 222.5 level alteration characterized by kaolinite and alunite (Malihan,
north); (B): Aggregates of fine-grained pyrite (py) in 1987). In addition, the occurrence of coarse-grained enar-
chalcopyrite (cp) in stockwork quartz veinlet associated gite in kaolinite alteration has been noted in the shallow
with sericite alteration envelope (#10324, 222.5 level part of the deposit (T. D. Malihan, pers. comm.).
north). Likewise, stibnite also occurs in vuggy quartz veinlets in
the shallow part of the deposit (T. D. Malihan, pers.
ation of aforementioned stringer veinlets of chalcopy- comm.). Stibnite occurs as needle-shaped up to 1 cm long
rite, pyrite and marcasite. It consists mainly of chal- crystals in vugs of vuggy quartz veinlets in which quartz
copyrite associated with subordinate pyrite and marca- exhibits saccharoidal-botryoidal habit.
site with trace of native gold (Table 3). A relatively
coarse (150 µm long) grain of native gold attached to 7. Diatreme and Pebble Dikes
euhedral coarse pyrite grain (0.5 mm across) in the
chalcopyrite matrix was observed (Fig. 7A). In addition The southern part of the fringe ore was largely
to coarse-grained euhedral pyrite grains, spherical destroyed by the post ore “Pua Diatreme”, in addition to a
aggregates of fine-grained pyrite are also observed in number of irregular bodies of pebble dikes (Fig. 3). Some
chalcopyrite matrix (Fig. 7B). of these pebble dikes have tabular geometry trending EW
vol. 55, no. 2, 2005 Dizon Porphyry Cu-Au Deposit, Philippines 81

Table 4 Chemical composition of tetrahedrite-group mineral (tennantite), Dizon porphyry Cu-Au deposit.
Sample ID Cu Ag Fe Zn Cd As Sb V S Se Total
wt% 41.85 0.92 4.52 0.21 0.33 17.23 7.67 0.03 27.95 0.03 100.74
041103
(atom%) (34.30) (0.45) (4.22) (0.17) (0.15) (11.98) (3.28) (0.03) (45.40) (0.02) (100)
Determined by electron probe microanalyzer, JEOL JCMA 733 markII, using accelerating voltage of 25kV and probe current of
2.0×10-8 A. The results were calibrated by conventional ZAF correction.
Sample Description:
041103: Tetrahedrite group mineral (tennantite) which exhibits micrographic intergrowth with galena in the WNW-trending late
stage quartz vein (225 level, north).

to WNW, and connect into the EW- to WNW-trending stage 1 sulfide

fractures, associated with Pb-Zn bearing veins. The peb- sulfate (gypsum)
ble dikes consist mainly of angular breccia clasts some-
times up to >20 cm across of country rocks to the pebble
dikes, i.e., altered andesitic rocks or altered quartz diorite
porphyry, etc. These pebble dikes are usually breccia/  -5 ±0 +5 +10 +15
stage 2
clast-supported, and the breccias/clasts are locally coated
with film of coarse-grained gypsum crystals occasionally
up to >10 cm across; gypsum occurs irregular but contin-
uous veinlets through interstices between the
breccias/clasts within the pebble dike. These pebble dikes
Frequency

are thought to have been caused by hydrothermal erup-

tions during subsequent hydrothermal activity related to
the EW- to WNW-trending fracture controlled Pb-Zn vein
mineralization.
A columnar-jointed body (up to 200 m across) of
dacite porphyry that appears as a large block in the Pua
Diatreme (Figs. 2, 3), looks displaced and dislocated
from the main dacite porphyry body. Alteration of the
dacite porphyry is not significant, whereas veinlets of
gypsum and structure-controlled narrow zones of
advanced argillic alteration crosscut the Pua Diatreme.
8. Sulfur Isotopes
The determined δ34S values are presented in Table 5
and shown in histograms in Figure 8. The δ34S values
of sulfides are relatively uniform throughout the miner-
alization stages.
The δ34S values of chalcopyrite + bornite associated
with stockwork amethystic quartz veinlets range from
+1.9 ‰ to +3.8 ‰ (stage 1, Fig. 8). The δ34S values of
sulfides in “center-line” of stockwork quartz veinlets and
stringer veinlets in sericite alteration envelope range from
-0.6 ‰ to +4.6 ‰ (stage 2, Fig. 8). The δ34S values of
sulfides (sphalerite and pyrite) in WNW-trending quartz
veins range from +3.0 ‰ to +5.9 ‰ (stage 4, Fig. 8). On
the other hand, the δ34S values of stibnite and enargite
from shallow part of WNW-trending veins are +0.7 ‰
and -4.3 ‰, respectively (Table 5). The low δ34S value of
enargite associated with advanced argillic alteration sug-
gests sulfur isotope fractionation with aqueous sulfate in
hydrothermal solution. The δ34S value of molybdenite is
+4.8 ‰ (stage 3, Fig. 8). Considering sulfur isotopic frac-
tionation between molybdenite and aqueous sulfide
 -5 ±0 +5 +10 +15
stage 3
 -5 ±0 +5 +10 +15
stage 4
 -5 ±0 +5 +10 +15
δ34S (‰)
Fig. 8 Histograms of sulfur isotope ratios of ore sulfides
of the Dizon porphyry Cu-Au deposit.
(Ohmoto and Goldhaber, 1997), the δ34S value of aque-
ous sulfide responsible for molybdenite is estimated to be
around +3.7 ‰, assuming isotopic equilibrium at 360°C
estimated by fluid inclusion microthermometry (see fol-
lowing chapter). The δ34S values of gypsum and pyrite
veinlet in pebble dike are +15.7 ‰ and +2.8 ‰, respec-
tively. The difference of δ34S values between gypsum and
pyrite is 12.9 ‰, corresponding to 460°C, assuming equi-
librium in sulfur isotopic fractionation (Ohmoto and
Goldhaber, 1997). This seems too high considering the
mode of occurrence of late stage veinlet in the post ore
pebble dike, and may suggest isotopic disequilibrium.
The majority of the sulfur isotopic composition of sul-
fides ranges from ±0 to +5 ‰, relative to CDT, whole
through paragenetic sequence except for fracture con-
trolled late stage mineralization trending WNW, especial-
ly for the enargite from the shallower part of the deposit.
82 Akira IMAI RESOURCE GEOLOGY :

Table 5 Sulfur isotope ratios, Dizon porphyry Cu-Au deposit.

Sample ID Mineral Stage δ34S(‰) Description
021220a pyrite 2 +0.8 disseminated
021220b pyrite+marcasite+chalcopyrite 2 +2.8 in stockwork quartz veinlets
021220c pyrite+marcasite+chalcopyrite 2 +2.5 in stockwork quartz veinlets
051220a pyrite 4 +2.8 in gypsum veinlet
051220b gypsum 4 +15.7 veinlet associated with pyrite
011103 chalcopyrite+bornite 1 +3.8 in stockwork quartz veinlets
041103d sphalerite 4 +5.2 in vuggy quartz vein
011104b pyrite 2 +3.7 stringer veinlet
011104c pyrite 2 +4.3 in stockwork vuggy quartz veinlet
031104 chalcopyrite+bornite 1 +2.2 in stockwork quartz veinlets
101104a sphalerite 4 +5.9 in vuggy quartz vein
101104b pyrite 4 +3.6 in vuggy quartz vein
101104c pyrite 4 +3.0 stringer veinlet
111104a sphalerite 4 +4.3 in vuggy quartz vein
111104b sphalerite 4 +3.2 in vuggy quartz vein
111104c sphalerite 4 +5.1 in vuggy quartz vein
111104d pyrite 4 +5.2 in vuggy quartz vein
161104a pyrite+marcasite 2 +4.4 in stockwork vuggy quartz veinlet
011105 chalcopyrite+pyrite 2 +3.8 in stockwork vuggy quartz veinlet
021105 chalcopyrite 2 +1.2 in stockwork vuggy quartz veinlet
041105 pyrite 2 +3.7 stringer veinlet
061105a chalcopyrite 2 +4.1 stringer veinlet
061105b pyrite 2 +2.0 stringer veinlet
081105 chalcopyrite+bornite 1 +3.0 in stockwork quartz veinlets
151105b pyrite+chalcopyrite 2 +3.6 in stockwork vuggy quartz veinlet
161105a pyrite+chalcopyrite 2 +4.3 stringer veinlet
161105b pyrite+chalcopyrite 2 +4.6 in stockwork vuggy quartz veinlet
171105 pyrite 2 +2.6 in stockwork vuggy quartz veinlet
221105 chalcopyrite+pyrite 2 +1.6 in stockwork vuggy quartz veinlet
231105 pyrite 2 -0.6 stringer veinlet
021106 pyrite 2 +2.9 stringer veinlet
071106 molybdenite 3 +4.8 in stringer quartz veinlet
02324b pyrite 2 +4.2 in stockwork vuggy quartz veinlet
03324a chalcopyrite+bornite 1 +1.9 in stockwork quartz veinlets
03324b pyrite 2 +4.3 stringer veinlet
10324c chalcopyrite+pyrite+marcasite 2 +2.8 veinlet
17324b pyrite 2 +1.4 in stockwork vuggy quartz veinlet
A stibnite 4 +0.8 vuggy veinlet
B enargite 4 -4.4 veinlet
Localities of samples collected from the open pit are shown in Figure 3. A, B: courtesy by Mr. T. D. Malihan.

Thus the sulfur isotopic composition of H2S and the ratio
of aqueous sulfate (SO4=) and H2S in the hydrothermal
fluids are supposed to have been relatively constant dur-
ing mineralization sequences except such late stage
hydrothermal activity. The average δ34S value of sulfides
throughout the mineralization stages is +3.0 ‰, and thus
the δ34S value of the mineralizing system seems to be
>±0 ‰. Sulfur originated from an isotopically uniform
and homogeneous source, and the mineralization
occurred in a single hydrothermal system.
The lightest isotopic value is obtained for enargite,
whereas those of sphalerite are the heaviest. The lightest
value of enargite can be interpreted by sulfur isotopic
fractionation with predominant aqueous sulfate at a
lower temperature, suggested by associated advanced
argillic alteration including alunite. The heavier sulfur
isotopes of sphalerite may imply the lesser amount of
oxidized aqueous sulfur species in deeper part.
9. Fluid Inclusion Microthermometry
Results of fluid inclusion microthermometry on veinlet
quartz are summarized in histograms in Figure 9. All the
examined fluid inclusions are classified as primary inclu-
sions based on the criteria of Roedder (1984). Most sam-
ples consist of polyphase fluid inclusions having NaCl
daughter crystals, so that only heating experiment has
been performed for the most cases in order to obtain the
vapor-liquid homogenization temperatures (Th) and the
dissolution temperatures of halite daughter crystal
(Tm NaCl) corresponding to the salinity. One sample
(#111104) consists of two-phase liquid-rich inclusions,
so that heating and freezing experiments were carried
out to obtain the vapor-liquid homogenization tempera-
vol. 55, no. 2, 2005 Dizon Porphyry Cu-Au Deposit, Philippines
tures (Th) and final ice melting point temperature (Tm)
corresponding to salinity, respectively.
Fluid inclusions found in stockwork veinlet quartz
associated with chalcopyrite, bornite and magnetite
assemblage consist of gas-rich inclusions and polyphase
inclusions composed of a transparent daughter salt crys-
tal presumably of halite, one or more minute bleb(s) of
opaque mineral (Fig. 10A) and/or transparent dark red-
dish hexagonal flake presumably of hematite (Fig. 10B),
and interstitial brine. Thus, hydrothermal fluids were
entrapped in an aqueous fluid immiscible region into
hypersaline brine and dilute vapor. Halite daughter salts
of polyphase inclusions dissolve at temperatures higher
than 360°C and mostly >500°C but liquid (brine) and
gas (vapor) do not homogenize up to 500°C (Fig. 9)
(#011103, #041104, #081105). Based on the dissolution
temperatures of halite daughter crystals in polyphase
fluid inclusions, the salinity is estimated to be >60 wt%
(>500°C, #011103), >51wt% (>440°C, #041104) and
>43 wt% (>360°C, #081105) (e.g., Sourirajan and
Kennedy, 1962). The formation temperature of stock-
work veinlet quartz associated with chalcopyrite, bor-
nite and magnetite is assumed to be 500°C in the discus-
sion in the following chapter, whereas the actual forma-
tion temperature are considered to be >500°C.
Fluid inclusions in stockwork veinlet quartz enveloped
in sericite alteration consist of gas-rich inclusions and
polyphase inclusions with variable abundance ratio. The
polyphase inclusion consists of a transparent crystal pre-
sumably of halite, occasionally one or more minute
bleb(s) of opaque mineral and/or transparent dark reddish
hexagonal flake presumably of hematite, and interstitial
brine. The temperatures of halite dissolution and liquid
vapor homogenization of the polyphase inclusions range
widely, from 230°C to >500°C and from 270°C to
>500°C, respectively (Fig. 9; #021105, #071104,
#021220, #10324, #03324, #09324, #161104, #011105,
#061105, #151105, #161105, and #171105). These wide
temperature ranges obtained from each veinlet quartz may
be explained by heterogeneous entrapment of gaseous
vapor and hypersaline brine at variable ratios. In addition,
the liquid-vapor homogenization temperatures are often
lower than the halite dissolution temperatures (#021220,
#09324, #161105). Thus, the hypersaline brine was satu-
rated with respect to NaCl at the time of entrapment.
Similar phenomena have been reported from the Mamut
deposit, Sabah, East Malaysia (Nagano et al., 1977; Imai,
2000a) and from the Lepanto-FSE deposit, Philippines
(Imai, 2000b).
Fluid inclusions in stringer veinlet quartz associated
with molybdenite consist mainly of gas-rich inclusions
with subordinate liquid-rich inclusions. Liquid inclu-
sions homogenize between 360°C and 490°C (#071106,
Fig. 9). Judging from wide ranges of homogenization
83
temperatures and the coexistence of gas-rich inclusions,
entrapment of boiling hydrothermal solution is sup-
posed. Thus, the temperature of the formation of
stringer veinlet quartz associated with molybdenite is
estimated to be about 360°C.
Fluid inclusions of vuggy quartz veinlets associated
with needle-shaped stibnite are dominated by gas-rich
inclusions with subordinate polyphase inclusions consist-
ing of a transparent daughter salt presumably of halite and
interstitial brine. Most polyphase inclusions do not homo-
genize below 500°C either by dissolution of halite daugh-
ter crystal or disappearance of vapor bubble (#A, Fig. 9).
Fluid inclusions in veinlet quartz associated with galena
and sphalerite are composed of two-phase inclusions hav-
ing various liquid-vapor ratios though dominated by liq-
uid-rich ones. They homogenize into liquid phase at tem-
peratures ranging widely from 190°C to 300°C (#111104,
Fig. 9). The final ice melting temperature ranges from -
0.6°C to -2.0°C and the corresponding salinity ranges
from 1.0 wt% to 3.4 wt% NaCl equivalent (#111104, Fig.
9). Judging from wide ranges of homogenization tempera-
tures as well as various liquid-vapor ratios, entrapment of
boiling hydrothermal solution is supposed. In addition,
boiling evidence is observed in vuggy quartz veinlets
associated with stibnite presumably precipitated roughly
in the same paragenetic stage at a shallower part. Thus,
whereas the liquid-vapor homogenization temperatures
range from 190°C to 300°C, the temperature of hydrother-
mal solution that deposited veinlet quartz associated with
galena and sphalerite is considered to be around 190°C.
10. Discussion
10.1. Initial porphyry Cu-Au mineralization
Porphyry Cu system is an evolving hydrothermal sys-
tem through multiple paragenetic sequences initiated
from the high-temperature magmatic hydrothermal sys-
tem. At the Dizon deposit, stockwork and sheeted thin
quartz veinlets are considered to be the products of ini-
tial high-temperature magmatic hydrothermal system.
Dissemination and stringer of magnetite are associated
with stockwork amethystic quartz veinlets in the central
portion of the biotitized and/or chloritized orebody
along with Cu-Fe sulfides such as chalcopyrite and bor-
nite which intimately exhibit micrographic intergrowth
texture (Fig. 5A, B), associated with fine-grained native
gold/Au-rich electrum as inclusions in Cu-Fe sulfides.
The association of Au with chalcopyrite and bornite
intergrowth resembles to the Cu sulfide ore associated
with anhydrite (-quartz) veinlets at the Santo Tomas II
deposit (Imai, 2001). Chalcopyrite and bornite inter-
growth is associated with magnetite within stockwork
and sheeted veinlet quartz at the Dizon while the inter-
growth of chalcopyrite and bornite is hosted commonly
84 Akira IMAI RESOURCE GEOLOGY :

011103 021105
polyphase inclusion polyphase inclusion
x opaque mineral opaque mineral
dissolution temperature of NaCl daughter crystal dissolution temperature of NaCl daughter crystal

Frequency
100 200 300 400 500
vapor-liquid homogenization temperature
Frequency

100 200 300 400 500

vapor-liquid homogenization temperature

100 200 300 400 500

Temperature (°C)
071104
polyphase inclusion
opaque mineral
dissolution temperature of NaCl daughter crystal

Frequency
100 200 300 400 500
Temperature (°C)
041104 100 200 300 400 500
polyphase inclusion vapor-liquid homogenization temperature
opaque mineral
dissolution temperature of NaCl daughter crystal

100 200 300 400 500

Temperature (°C)
Frequency

021220
polyphase inclusion
100 200 300 400 500 dissolution temperature of NaCl daughter crystal
vapor-liquid homogenization temperature

100 200 300 400 500

Temperature (°C)
081105
polyphase inclusion
opaque mineral
Frequency

dissolution temperature of NaCl daughter crystal

100 200 300 400 500

vapor-liquid homogenization temperature
Frequency

100 200 300 400 500

vapor-liquid homogenization temperature

100 200 300 400 500

Temperature (°C)

Fig. 9 Histograms showing the results of fluid inclusion

microthermometry of the Dizon porphyry Cu-Au deposit.
Plots above 500˚C represent inclusions that do not homog-
enize at <500˚C. Data of gas-rich inclusions are not
shown. Localities of samples collected from the open pit
are shown in Figure 3.
100 200 300 400 500
Temperature (°C)
vol. 55, no. 2, 2005 Dizon Porphyry Cu-Au Deposit, Philippines 85

10324 061105
polyphase inclusion polyphase inclusion
opaque mineral dissolution temperature of NaCl daughter crystal
dissolution temperature of NaCl daughter crystal

Frequency
100 200 300 400 500
vapor-liquid homogenization temperature
Frequency

100 200 300 400 500

vapor-liquid homogenization temperature

100 200 300 400 500

Temperature (°C)
100 200 300 400 500 151105
Temperature (°C) polyphase inclusion
03324 opaque mineral
polyphase inclusion dissolution temperature of NaCl daughter crystal
opaque mineral
dissolution temperature of NaCl daughter crystal

Frequency
v 100 200 300 400 500
vapor-liquid homogenization temperature
Frequency

100 200 300 400 500

vapor-liquid homogenization temperature

100 200 300 400 500

Temperature (°C)
09324 100 200 300 400 500
polyphase inclusion Temperature (°C)
opaque mineral 161105
dissolution temperature of NaCl daughter crystal polyphase inclusion
opaque mineral
Frequency

dissolution temperature of NaCl daughter crystal

100 200 300 400 500

vapor-liquid homogenization temperature
Frequency

100 200 300 400 500

Temperature (°C)
161104 100 200 300 400 500
polyphase inclusion vapor-liquid homogenization temperature
dissolution temperature of NaCl daughter crystal
Frequency

100 200 300 400 500

100 200 300 400 500
vapor-liquid homogenization temperature
Temperature (°C)
171105
polyphase inclusion
100 200 300 400 500 dissolution temperature of NaCl daughter crystal
Temperature (°C)
011105
Frequency

polyphase inclusion
Frequency

dissolution temperature of NaCl daughter crystal

100 200 300 400 500
vapor-liquid homogenization temperature
100 200 300 400 500
vapor-liquid homogenization temperature

100 200 300 400 500 100 200 300 400 500
Temperature (°C) Fig. 9 (continued) Temperature (°C)
86 Akira IMAI RESOURCE GEOLOGY :

071106 Sample description:

Frequency

liquid-rich two-phase inclusion

vapor-liquid homogenization temperature #011103: Magnetite-bearing amethystic stockwork quartz veinlet associat-
ed with chalcopyrite and bornite (Figs. 6A, B) (237.5 level, center).
#041104: Magnetite-bearing amethystic stockwork quartz veinlet associat-
ed with native gold/Au-rich electrum in chalcopyrite and bornite (Fig.
100 200 300 400 500 5A, B) (237.5 level, southwest).
Temperature (°C) #081105: Magnetite-bearing amethystic stockwork quartz veinlet associat-
A
polyphase inclusion ed with chalcopyrite and bornite (250 level, south).
dissolution temperature of NaCl daughter crystal #021105: Vuggy quartz veinlet associated with chalcopyrite (250 level,
southwest).
#071104: Sheeted stringer quartz veinlet associated with chalcopyrite
(237.5 level, west).
Frequency

#021220: Marcasite, pyrite and chalcopyrite-bearing stockwork quartz

100 200 300 400 500 veinlet associated with sericite alteration envelope (275 level, west).
vapor-liquid homogenization temperature #10324: Stockwork quartz veinlet associated with marcasite, pyrite and
chalcopyrite and native gold/Au-rich electrum in sericite alteration enve-
lope (Fig. 6A) (222.5 level, north).
#03324: Quartz veinlet filling interstices in brecciated andesite (222.5
level, north).
100 200 300 400 500 #09324: Quartz veinlet filling interstices between brecciated andesite
Temperature (°C) (222.5 level, north).
111104 #161104: Marcasite and pyrite-bearing stockwork quartz veinlet associated
Frequency

liquid-rich two-phase inclusion with sericite alteration envelope (225 level, northwest).
salinity
#011105: Vuggy quartz veinlet associated with chalcopyrite and pyrite ore
in sericite alteration envelope (250 level, southwest).
0 1 2 3 4 #061105: Sheeted and stockwork stringer quartz veinlet associated with
wt% (NaCl equivalent) chalcopyrite stringers (250 level, south).
#151105: Vuggy quartz veinlet associated with chalcopyrite and pyrite ore
111104 in sericite alteration envelope (250 level, east).
Frequency

liquid-rich two-phase inclusion #161105: Vuggy quartz veinlet associated with chalcopyrite and pyrite ore
vapor-liquid homogenization temperature
in sericite alteration envelope (250 level, east).
#171105: Vuggy quartz veinlet associated with pyrite (250 level, east).
#071106: Molybdenite-bearing stringer quartz veinlet in sericite alteration
envelope (300 level, west).
100 200 300 400 500 #A: Stibnite and pyrite-bearing stringer quartz vuggy veinlet in sericite
Temperature (°C) alteration envelope.
Fig. 9 (continued) #111104: Sphalerite and galena-bearing quartz veinlet (250 level, east).

Fig. 10 Photomicrographs of polyphase fluid inclusions in magnetite-bearing amethystic stockwork quartz veinlet associated
with chalcopyrite, bornite and magnetite (#011103; 237.5 level, center). (A): Polyphase inclusion consists of halite daughter
crystal (ha), vapor bubble (v), opaque mineral (op) and brine. (B): Polyphase inclusion consists of halite daughter crystal
(ha), vapor bubble (v), hematite (hm) and brine.

in anhydrite veinlet and is not associated with Fe oxide
at the Santo Tomas II deposit (Imai, 2001). The coexis-
tence of chalcopyrite and bornite indicate that the bulk
composition of the sulfide ore lies near the bornite-chal-
copyrite tie-line in the Cu-Fe-S ternary system (e.g.,
Yund and Kullerud, 1966). Thus, the bulk composition
of this type ore is rich in Cu (the Cu/Fe ratio is higher
than 1) than the composition of chalcopyrite.
Considering the stability of assemblage of chalcopyrite
and bornite solid solution (bnss) (Barton, 1973) and the
vol. 55, no. 2, 2005 Dizon Porphyry Cu-Au Deposit, Philippines
estimated formation temperature based on fluid inclusion
microthermometry on polyphase fluid inclusions in veinlet
quartz, chalcopyrite is not likely to have been a primary
phase. The primary assemblages is thought to have includ-
ed intermediate solid solution (iss) phase, which then
underwent subsequent exsolution reaction to form the pre-
sent chalcopyrite-bearing assemblages during cooling.
Primary bnss and iss may convert to the present assem-
blage of bornite and chalcopyrite.
10.2. Overprinting hydrothermal systems
A lot of attention are focused on the spatial and tempo-
ral, hence, genetic relationships between the porphyry Cu
deposit and nearby epithermal system of especially classi-
fied as acid-sulfate (Heald et al., 1987) or high-sulfidation
(Hedenquist, 1987) type, with particular interest placed on
evolution of hydrothermal system, i.e., transition from
porphyry-type high temperature magmatic hydrothermal
system to epithermal system. The Dizon deposit is consid-
ered as a good representative instance of subvolcanic
hydrothermal system for the advanced argillic alteration
blanket of high-sulfidation assemblage accompanying
enargite/stibnite mineralization, and diatreme and
hydrothermal breccia pipes (pebble dikes), suggesting
shallow depth of formation under subvolcanic environ-
ment (Malihan, 1982, 1987; Sillitoe and Gappe, 1984).
Parts of the high grade Cu-Au ore are form of stock-
work quartz veinlets enveloped in sericite alteration.
Quartz sometimes appears chalcedonic-porcellaneous,
and marcasite occurs sometimes along with pyrite and
chalcopyrite in quartz veinlet stockwork in the sericite
alteration envelope. Further overprinting vein-type Pb-
Zn mineralizations occur spatially controlled by EW- to
WNW-trending faults/fissures and open space fractures
are thought to be formed in epithermal environment,
based on quartz textures and fluid inclusions microther-
mometry as well. These EW- to WNW-trending veins
grade into stibnite and enargite-bearing surrounded by
advanced argillic alteration at shallow levels.
A whole-rock K/Ar age on the potassically altered fine-
grained diorite porphyry from the orebody center, in
which hornblende phenocrysts are replaced by aggregates
of fine-grained hydrothermal biotite, yields 2.5±0.2 Ma,
which is in good agreement with the previously reported
K/Ar age of 2.7 Ma determined for hydrothermal sericite
(Malihan, 1987). The age of the Dizon deposit is about
2.5±0.2 Ma both for the initial biotite alteration and the
subsequent sericite alteration, and maybe for the over-
printing advanced argillic alteration. Similarly, Arribas et
al. (1995) reported contemporaneous formation of the
Lepanto-FSE porphyry Cu-Au deposit and the Lepanto
high-sulfidation epithermal Cu-Au deposit (Garcia, 1991;
Imai, 1999) at Mankayan district. In addition, the age of
the Victoria low-sulfidation epithermal Au deposit
87
(Claveria, 2001; Sajona et al., 2002) was also considered
to be contemporaneous with Lepanto-FSE porphyry Cu-
Au deposit and the Lepanto high-sulfidation epithermal
Cu-Au deposit (Sajona et al., 2002).
The majority of the sulfur isotopic composition of sul-
fides ranges from ±0 ‰ to +5 ‰, whole through parage-
netic sequence except for fracture controlled late stage
mineralization. Sulfur originated from an isotopically uni-
form and homogeneous source, and the hydrothermal
activity occurred in a single hydrothermal system.
Fluid inclusions found in stockwork veinlet quartz ini-
tially associated with iss, bnss and magnetite consist of
gas-rich inclusions and polyphase inclusions. Thus,
hydrothermal fluids were entrapped in the aqueous fluid
immiscible region into hypersaline brine and dilute vapor.
The aqueous fluid immiscible region into hypersaline
brine and dilute vapor at 500°C is encountered at pressure
below about 600 bars (Sourirajan and Kennedy, 1962).
Thus, the pressure estimated for the hydrothermal system
during the deposition of iss, bnss and magnetite with
stockwork quartz veinlets seems to be lower than 600 bars
at 500°C. Furthermore, based on the estimated salinities,
>60 wt% (#011103), >51wt% (#041104) and >43 wt%
(#081105) at 500°C, the maximum pressures where the
corresponding hypersaline brine immiscible with dilute
vapor are estimated to be about 330 bars, 400 bars and
460 bars, respectively (Sourirajan and Kennedy, 1962).
Thus, the maximum pressure during the deposition of iss
and bnss with stockwork quartz veinlets seems to be lower
than 460 bars, probably lower than 330 bars, at 500°C.
Fluid inclusions in veinlet stockwork quartz enveloped
in sericite alteration consist of gas-rich inclusions and
polyphase inclusions. In addition to the possible presence
of saturated NaCl crystals at the time of entrapment of
fluid inclusions that exhibit the liquid-vapor homogeniza-
tion temperatures lower than the halite dissolution temper-
atures in some samples (#021220, #09324, #161104),
wide range of temperatures of halite dissolution and liq-
uid-vapor homogenization of polyphase inclusions from
230°C to >500°C and from 245°C to >500°C, respective-
ly, suggests heterogeneous entrapment of inclusion fluids
of gaseous vapor and hypersaline brine at variable ratios.
Thus, the lowest temperature of the range of liquid-vapor
homogenization temperature of polyphase inclusions can
be regarded as the temperature of hydrothermal solution
during the precipitation of veinlet stockwork quartz
enveloped in sericite alteration. The aqueous fluid immis-
cible region into hypersaline brine and dilute vapor
encountered at 245°C suggests the minimum pressure to
be about 25 bars based on the liquid-vapor-halite three
phase line (Fig. 11) assuming the saturation of NaCl
(Roedder and Bodnar, 1980, 1997).
Whereas liquid-rich two-phase fluid inclusions in vein-
let quartz associated with galena and sphalerite that
88
critical point curve
Pressure (bar)
critical point of pure water
boiling point curve
of pure water liquid-vapor-halite
three phase curve
Temperature (°C)
Fig. 11 Relationships between homogenization tempera-
ture and pressure deduced from fluid inclusion
microthermometry. The boiling point curve of pure
water (Haas, 1971), the critical point curve originating
from the critical point of pure water (Sourirajan and
Kennedy, 1962) and the liquid-vapor-halite three phase
line (Roedder and Bodnar, 1980, 1997) are illustrated
for reference. Symbols: solid circle (●): stage 1 stock-
work amethystic veinlet quartz associated with mag-
netite, chalcopyrite and bornite (samples #011103,
#041104, #081105), solid diamond (◆): stage 2 stock-
work veinlet quartz with sericite alteration envelope
(#021105, #071104, #021220, #10324, #03324,
#09324, #161104, #011105, #061105, #151105,
#161105, #171105), open diamond ( ◇ ): stage 3
molybdenite-bearing stringer quartz veinlet in sericite
alteration envelope (#071106), open square (□): stage
4 WNW-trending vein quartz associated with stibnite
(#A) and with sphalerite and galena (#111104).
homogenize into liquid phase at temperatures ranging
widely from 190°C to 300°C (#111104, Fig. 9) the tem-
perature of hydrothermal is considered to be around
190°C since the entrapment of boiling hydrothermal solu-
tion is supposed. For the dilute aqueous solution for the
liquid-rich fluid inclusions (salinity ranging from 1.0 wt%
to 3.4 wt% NaCl equivalent: #111104, Fig. 9), a depth of
about 15 bars for 190°C (Haas, 1971; Roedder and
Bodnar, 1980; Roedder, 1984) is estimated for the
hydrothermal fluid that precipitated veinlet quartz associ-
ated with galena and sphalerite (Fig. 11).
Relationships between homogenization temperature and
pressure deduced from fluid inclusion microthermometry
are shown in Figure 11. The lowest liquid-vapor homoge-
nization temperature and corresponding pressure estimat-
ed are plotted. The boiling point curve of pure water
(Haas, 1971), the critical point curve originating from the
critical point of pure water (Sourirajan and Kennedy,
1962) and the liquid-vapor-halite three phase line (Roedder
and Bodnar, 1980, 1997) are also illustrated for reference.
Akira IMAI RESOURCE GEOLOGY :
The quartz veinlets associated with sphalerite and galena
containing only vapor-liquid two phase are plotted along
the boiling point curve of pure water as the inclusion fluids
are presumed to be dilute aqueous fluid. Likewise, the
quartz veinlet associated with molybdenite containing liq-
uid-vapor two phase inclusions is also plotted along the
boiling point curve of pure water assuming dilute aqueous
fluid. On the other hand, most of the quartz veinlets having
polyphase inclusions, except for those associated with
magnetite, chalcopyrite and bornite, are plotted along the
liquid-vapor halite curve. Since both the vapor-liquid
homogenization temperature and dissolution temperature
show wide range, the lowest vapor-liquid homogenization
temperatures are considered as the formation temperatures,
and thus, the brine is considered to have saturated with
NaCl, in addition to the possible presence of saturated
NaCl crystals at the time of entrapment of fluid inclusions
that exhibit the liquid-vapor homogenization temperatures
lower than the halite dissolution temperatures in some
quartz veinlets enveloped in sericite alteration.
A change in temperature-pressure regime from litho-
static pressure during the deposition of iss and bnss with
stockwork quartz veinlets to hydrostatic pressure during
fracture-controlled quartz veinlet associated with galena
and sphalerite is most likely. However, this simple
change from lithostatic to hydrostatic cannot account for
the change from 600 bars to 15 bars, because such
change in pressure media may account for the change in
pressure from 460 bars to about 150 bars at the same
depth considering the density difference between litho-
static lode and the aqueous solution.
The southern part of the fringe ore was largely
destroyed by the post ore “Pua Diatreme”, in addition to a
number of irregular bodies of pebble dikes. These pebble
dikes are thought to have formed simultaneously with
hydrothermal activity related to Pb-Zn vein mineraliza-
tion. Diatreme which destroyed initial porphyry Cu ore-
body has been documented from a number of porphyry
Cu deposit, such as El Teniente deposit, Chile (e.g.,
Camus, 1975; Kusakabe et al., 1984). Sillitoe (1994)
emphasized that collapsing of volcanic landform, during
magmatic hydrothermal system of porphyry Cu mineral-
ization is active underneath, results in the telescoping
epithermal system such as the Ladolam deposit, Lihir
Island. A decrease in pressure is supposed to have
occurred due to unroofing or removal of the overlying
piles during the temperature decrease in the evolution of
hydrothermal system at the Deposit.
11. Summary and Conclusions
The paragenetic stages throughout the Dizon porphyry
Cu-Au deposit are summarized as follows; 1) stockwork
amethystic quartz veinlets associated with chalcopyrite-
vol. 55, no. 2, 2005 Dizon Porphyry Cu-Au Deposit, Philippines
bornite-magnetite and Au in chlorite alteration envelope,
2) stockwork quartz veinlets with chalcopyrite and pyrite
“center-line” associated with Au and chalcopyrite and
pyrite stringers in sericite alteration, 3) stringer quartz
veinlet associated with molybdenite in sericite alteration
and 4) WNW-trending quartz veins associated with spha-
lerite and galena at deeper part, while enargite and stibnite
at shallower levels associated with advanced argillic alter-
ation.
The chalcopyrite and bornite associated with magnetite
in quartz veinlet stockwork have precipitated as iss and
bnss initially and converted to the present assemblage dur-
ing cooling. The maximum pressure and minimum tem-
perature estimated for the hydrothermal system during the
deposition of iss and bnss with stockwork quartz veinlets
seem to be 460 bars and 500°C.
In addition to the possible presence of saturated NaCl
crystals at the time of entrapment of fluid inclusions that
exhibit the liquid-vapor homogenization temperatures
lower than the halite dissolution temperatures in some
samples, wide range of temperatures of halite dissolu-
tion and liquid-vapor homogenization of polyphase
inclusions in veinlet stockwork quartz enveloped in
sericite alteration suggests heterogeneous entrapment of
gaseous vapor and hypersaline brine. The minimum
pressure and temperature are estimated to be about 25
bars and 245°C, during precipitation of quartz veinlets
enveloped in sericite alteration.
Fluid inclusions in veinlet quartz associated with galena
and sphalerite are composed of liquid-rich two-phase
inclusions having various liquid-vapor ratios, and they
homogenize into liquid phase at temperatures ranging
widely from 190°C to 300°C (suggesting boiling) and the
salinity ranges from 1.0 wt% to 3.4 wt% NaCl equivalent.
Thus, a pressure of about 15 bars is estimated for the
dilute aqueous solution of 190°C from which veinlet
quartz associated with galena and sphalerite precipitated.
During the temperature decrease in the evolution of
hydrothermal system, a decrease in pressure is supposed
to have occurred. A change in temperature-pressure
regime from lithostatic pressure during the deposition of
iss and bnss with stockwork quartz veinlets to hydrostatic
pressure during fracture-controlled quartz veinlet associat-
ed with galena and sphalerite is most likely. However, this
simple change from lithostatic to hydrostatic cannot
account for the change from 460 bars to 15 bars, and a
decrease in pressure is supposed to have occurred due to
unroofing or removal of the overlying piles.
The majority of the sulfur isotopic composition of sul-
fides ranges from ±0 ‰ to +5 ‰. Sulfur originated from
an isotopically uniform and homogeneous source, and the
mineralization occurred in a single hydrothermal system.
Acknowledgments: I thank the Mines and Geosciences
Bureau, Philippines, Benguet Corporation. R. L. Almeda,
89
J. S. Aquino, H. E. A. Franco, S. Ishihara, E. Izawa, Y.
Kajitani, E. L. Listanco, T. D. Malihan, H. Matsueda, A.
B. Sajona, H. Shimazaki, R. H. Sillitoe, T. Suzuki, R. I.
Villones, Jr., and G. P. Yumul, Jr. are appreciated for
warm support and encouragement, constructive sugges-
tions and discussions. The stibnite and enargite samples
were courtesy of T. D. Malihan. Critical comments by
Resource Geology reviewers improved this paper signifi-
cantly.
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